Silver halide element containing polymeric colour forming couplers

ABSTRACT

Light-sensitive photographic colour elements are described containing polymeric compounds comprising recurring colour coupler or competing coupler units and units derived from a monomer corresponding to the formula:   wherein: R is hydrogen, C1-C4 alkyl or chlorine, X is -O- or -N(R&#39;&#39;)- wherein R&#39;&#39; is hydrogen or lower alkyl, Y is a divalent hydrocarbon group which may be interrupted by oxygen and/or sulphur, and M is a cation. The polymeric compounds can be incorporated in hydrophilic colloid coating compositions from latices that do not contain ballasting emulsifying agents, show less foaming tendency, have high compatibility with hydrophilic colloids such as gelatin and make possible to coat thinner layers.

'United States Patent Monbaliu et al.

[ Dec. 16, 1975 22 Filed: Feb. 15, 1974 21 Appl. No.: 443,118

[30] Foreign Application Priority Data Feb. 26, 1973 United Kingdom9421/73 [52] U.S. Cl. 96/67; 96/74; 96/100;

[51] Int. Cl. G03C 1/40; 603C H72 [58] Field of Search 96/100, 114, 67

[56] References Cited UNITED STATES PATENTS 2,353,262 7/1944 Peterson etal. 96/100 2,976,294 3/1961 Firestine 96/100 3,024,221 3/1962 LeFevre eta1. 260/793 MU 3,356,686 12/1967 Firestine et a1. 96/100 3,370,9522/1968 Dawson 96/100 3,767,412 10/1973 Monbaliu et al 96/100 PrimaryExaminer-J. Travis Brown Attorney, Agent, or FirmRobert M. Ashen; RobertJ. Schaap [57] ABSTRACT Light-sensitive photographic colour elements aredescribed containing polymeric compounds comprising recurring colourcoupler or competing coupler units and units derived from a monomercorresponding to the formula:

wherein:

R is hydrogen, C -C alkyl or chlorine, X is -O or N(R) wherein R ishydrogen or lower alkyl, Y is a divalent hydrocarbon group which may beinterrupted by oxygen and/or sulphur, and M is a cation.

The polymeric compounds can be incorporated in hydrophilic colloid.coating compositions from latices that do not contain ballastingemulsifying agents, show less foaming tendency, have high compatibilitywith hydrophilic colloids such as gelatin and make possible to coatthinner layers.

9 Claims, No Drawings The present invention relates to polymeric colourforming couplers and competing couplers and to photographic silverhalide elements containing these polymeric compounds.

It is known that for the production of a photographic colour image in alight-sensitive silver halide emulsion layer the exposed silver halideis developed to a silver image by means of an aromatic primary aminocompound in the presence of a colour coupler which by reaction with theoxidized developer forms a dye on the areas corresponding to the silverimage.

It is also known to improve colour reproduction in photographic colourelements by incorporating therein so-called competing couplers whichreact with the oxidation products of the developing agent to formcolourless compounds. They are used in those instances where suchundesirable oxidation products should be rendered ineffective so thatdegradation of the image quality is inhibited. Colour couplers andcompeting couplers, when incorporated in photographic light-sensitivesilver halide material, should remain immobile and not wander or diffusethrough the material from their original site.

Besides colour couplers and competing couplers carrying in theirmolecule a long chain aliphatic group to prevent diffusion it has alsobeen proposed to use polymeric couplers obtained by additionpolymerization of monomeric couplers.

Polymeric couplers are preferably used in the form of latices obtainedby emulsion polymerization techniques with the aid of the usual additionpolymerization initiators. Interesting emulsion polymerisationtechniques are for instance described in Belgian Pat. No. 669,971according to which latices are formed of polymeric colour couplers byemulsion polymerisation in aqueous gelatin, and in United Kingdom Pat.No. 1,130,581 according to which latices are formed of polymericcouplers by emulsion polymerisation in water.

The incorporation of polymeric couplers in hydrophilic colloidcompositions in the form of latices have important advantages over theincorporation of the polymeric or nonpolymeric couplers in the form ofsolutions in water, water-miscible solvents or waterimmiscible solvents.

Indeed, latices may contain a high percentage of polymer e.g.concentrations up to 50 and nevertheless still possess a relatively lowviscosity; when incorporating said latices into emulsions the viscosityof the latter is not influenced. Moreover, by the use of latices therecan be dispensed with the use of organic solvents or alkaline solutionsas well as with special dispersing techniques for incorporating thecoupler compounds.

However, the use of latices also poses a number of difficulties. Forexample, it is often required to add an extra amount of emulsifyingagent when incorporating the latex into the hydrophilic colloidcomposition e.g. a silver halide emulsion in that the emulsifying agentused in the preparation of the latex does not suffice to stabilize thepolymer particles in the hydrophilic colloid. Moreover, the ballast ofemulsifying agent may give rise to foaming when dispersing the latex inthe hydrophilic colloid and the coated layer often shows repellencyspots, streaks and the like coating defects.

It is an object of the present invention to provide latices of polymericcolour couplers and competing couplers that are exempt from theotherwise ballasting emulsifying agents.

It is also an object of the present invention to provide latices ofpolymeric colour couplers and competing couplers wherein the polymerparticles are internally stabilized in the aqueous colloidal dispersionby a polymerically combined emulsifier.

Another object of the present invention is to provide latices ofpolymeric colour couplers and competing couplers that have reducedfoaming tendency and do not give rise to coating defects in hydrophiliccolloid coatings.

Still another object of the present invention is to provide latices ofpolymeric colour couplers and competing couplers which have highcompatibility with hydrophilic colloids more particularly gelatin and donot require an external surfactant for being dispersed into thehydrophilic colloid.

A further object is to provide latices of polymeric colour couplers andcompeting couplers which comprise reduced ballast of emulsifying agentso that it is possible to obtain thinner hydrophilic colloid layers e.g. silver halide emulsion layers which results in increased sharpness.

A still further object is to provide a photographic silver halide colourelement comprising in a silver halide emulsion layer or in a hydrophiliccolloid layer in water-permeable relationship with a silver halideemulsion layer, a said latex of a polymeric colour coupler or competingcoupler.

Other objects and advantages of the invention will become apparent fromthe description below.

The objects of the present invention have been attained in latices ofpolymeric compounds that are copolymers comprising recurring unitsderived from ethylenically unsaturated colour coupler or competingcoupler monomers and recurring units derived from monomers correspondingto the formula:

wherein:

R is hydrogen, alkyl, preferably C C, alkyl, or chlorme,

X represents -O- or N(R')-wherein R is hydro gen or lower alkyl e.g.methyl,

Y represents a divalent hydrocarbon group which may be interrupted byoxygen and/or sulphur e.g. alkylene, arylene e.g. phenylene,alkyleneoxyalkylene, alkylenephenylene and alkyleneoxyphenylene, inwhich the alkylene groups are preferably lower alkylene groups andinclude straight-chain and branched-chain alkylene, cycloalkylene andsubstituted alkylene e.g. alkylene substituted by halogen e.g. chlorineand bromine, alkoxy and phenyl, and in which the arylene groups includesubstituted arylene, and

M represents a cation e.g. hydrogen, a metal atom e.g. sodium andpotassium, ammonium and organic amine, e.g. diethanolamine,triethylamine.

Representative monomeric compounds corresponding to the above generalformula I can be found in British Pat. No. 1,009,186 and US. Pat. No.3,024,221. Particularly suitable results are obtained with mono- 3 mersin which Y stands for a straight-chain or branched-chain C C alkylenegroup i.e. with sulphoethyl, sulphopropyl and sulphobutyl esters ofacrylic acid and a-substituted acrylic acids and to a less degree withthe N-sulphoethyl, N-sulphopropyl and N-sulphobutyl acrylamides ora-substituted acrylamides.

The present invention thus provides latices of polymeric compounds thatare copolymers comprising recurring units derived from ethylanicallyunsaturated colour coupler or competing coupler monomers and recurringunits derived from monomers corresponding to the above formula.

The present invention further provides a photographic silver halidecolour element comprising a support and at least one silver halideemulsion layer wherein the said silver halide emulsion layer and/or ahydrophilic colloid layer in water-permeable relationship therewithcomprises a polymeric latex the polymer of which being a copolymer asdefined above.

As is known in the art the polymeric couplers may also comprise units ofcopolymerized ethylenically unsaturated monomers that are not capable ofoxidative coupling with aromatic primary amino compounds for exampleacrylic acid, a-chloroacrylic acid, a-alkacrylic acids, wherein thesubstituting alkyl contains from 1 to 4 carbon atoms e.g. methyl, ethyland n-propyl, the esters and amides derived from acrylic acid,a-chloroacrylic acid and these a-alkacrylic acids, such as acrylamide,methacrylamide, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylateand lauryl methacrylate, vinyl esters such as vinyl acetate, vinylpropionate and vinyl laurate, acrylonitrile, methacrylonitrile, aromaticvinyl compounds such as styrene and its derivatives, e.g. vinyl toluene,vinyl acetophenone and sulphostyrene, itaconic acid, citraconic acid,crotonic acid, vinylidene chloride, vinyl alkyl ethers such as vinylethyl ether, maleic acid esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinyl-pyridine.

As is known in the art, the ethylenically unsaturated monomers suitablefor being copolymerized with the monomeric colour couplers or competingcouplers and the monomeric sulphoesters or sulphoamides described abovecan be chosen so that the physical and/or chemical properties of theresulting copolymer such as its solubility, its flexibility, its thermalstability, etc., are favourably influenced. For example, it is knownthat methacrylic acid and styrene when used together as comonomers e.g.in a ratio of about to about 30 and about 50 to about 30 percent byweight respectively relative to the total amount of monomers giveparticularly good results in polymeric colour couplers in that theyyield dye images of improved sensitometric properties and improvedstability against moisture and heatv Other favourable comonomers areacrylic acids and acrylates either used alone or in combination.

The monomeric ethylenically unsaturated colour couplers or competingcouplers for being copolymerised in accordance with the presentinvention are generally of the type respresented by the formula II II Rwherein:

R is hydrogen, alkyl, preferably C -C alkyl, or chlorine 4 Q is a colourcoupler or competing coupler residue capable of coupling with anoxidized aromatic primary amine colour developing agent.

Colour couplers and competing couplers are well known in the art ofsilver halide colour photography. The monomers represented by the aboveformula II comprise a residue Q of well known coupler compounds forexample 1, a residue of a cyan-forming colour coupler of the phenol ornaphthol type e.g. of the formula:

wherein A is a single chemical bond or a bivalent organic group linkingthe ethylenically unsaturated group of the formula II to the colourcoupler residue,

R represents hydrogen, a substituent of the type well known in phenol ornaphthol colour couplers such as halogen alkyl or aryl, or the atomsnecessary to complete a fused-on benzene nucleus which may besubstituted, and

Y represents a hydrogen atom in the case of 4- equivalent couplers or asubstituent which splits off upon colour development thus conferring tothe colour coupler a 2-equivalent character e. g. a halogen atom such aschlorine, an acyloxy group, an alkoxy, aryloxy, or heterocycloxy group,an alkylthio, arylthio or heterocyclic thio group such as tetrazolylthiogroup, or phenylazo group etc.

2. a residue of a magenta-forming colour coupler of the pyrazolone orindazolone type e.g. of the formula:

wherein:

R is substituent of the type well-known in the l-position of2-pyrazolin5-one colour couplers e.g. alkyl including substituted alkyle.g. haloalkyl such as fluoroalkyl, cyanoalkyl and benzyl, or arylincluding substituted aryl e.g. phenyl which may be substituted byalkyl, halogen, alkoxy, haloalkoxy, alkyl sulphonyl, haloalkylsulphonyl, alkylthio, haloalkylthio, etc., and

Y is hydrogen in the case of 4-equivalent couplers or a substituentwhich splits off upon colour development thus conferring to the colourcoupler a 2-equivalent character e.g. a halogen atom such as chlorine,an acyloxy group, an alkoxy group, an aryloxy group or a heterocycloxygroup, an alkylthio group, an arylthio group or a heterocyclic thiogroup such as tetrazolylthio, a phenylazo group, etc.

3. a residue of a yellow forming colour coupler of the acylacetamidetype, especially the acylacetanilide type for example an anilinocarbonylacetophenyl group or a benzoylacetamidophenyl group wherein botharyl group may be substitutedby substituents well known inyellow-forming colour couplers e.g. alkyl, alkoxy, halogen, alkylthio,alkylsulphonyl, etc. and wherein the active methylene group may carry asubstituent conferring to the colour coupler a 2-equivalent charactere.g. a halogen atom such as chlorine, acyloxy, an alkoxy, aryloxy orheterocycloxy group, an alkylthio, arylthio or heterocyclic thio group,etc.

4. a competing coupler residue e.g. of the type described for the abovecolour couplers wherein one hydrogen atom of the active methylene groupis replaced by alkyl, preferably C -C alkyl including substituted alkyle.g. benzyl, preferably a competing coupler residue of the2-pyrazolin-5-one type.

Examples of monomeric colour couplers suitable for copolymerization inaccordance with the present invention can be found in the literaturee.g. in Belgian Pat. Nos. 584,494 602,516 and 669,971, in British Pat.Nos. 967,503 1,130,581 1,247,688 and 1,269,355, in U.S. Pat. No.3,356,686 and in British Pat. Application No. 59792/70.

Representative examples are:

Z-methylsulphonylamino-S-methacrylaminophenol2-methylsulphonylamino-4-chloro-5-methacrylaminophenol2-phenylsulphonylamino-5-methacrylaminophenol 2-(4-chlorophenyl)sulphonylamino-S-methacrylaminophenol 2-(4-sec.butylphenyl)crylaminophenol 2-ethoxycarbonylamino-S-methacrylaminophenol2-n-butylureido-5-methacrylaminophenol2-benzoylamino-5-methacrylaminophenol2-o-methylbenzoylamino-S-methacrylaminophenol2-acetylamino-5-methacrylaminophenolZ-p-methoxybenzoylamino-S-methacrylaminophenol2-o-chlorobenzoxylamino-5-methacrylaminophenol2-p-t.butylbenzoylamino-S-methacrylaminophenol 1-hydroxy-N-B-acrylamidoethyl-2-naphthamide1-hydroxy-N-B-vinyloxyethy1-2-naphthamide1-hydroxy-4-chlor0-N-B-methacrylamidoethyl-2- naphthamide 11-hydroxy-4-chloro-N-,B-acrylamidoethyl-2-naphthamide2-methacrylamido-4,6-dichloro-5-methylphenol1-benzyl-3-acrylamido-2-pyrazolin-5-one l-( 2-cyanoethyl )-3-methacrylamido-2-pyrazolin- 5-one 1-( 3 ,4-dichlorobenzyl )-3-methacrylamido-2-pyrazolin-5-one1-(2,2,2-trifluoroethyl)-3-methacrylamido-2-pyrazo lin-S-one 1-p-( l ,1,2-trifluoro-2-chloroethoxy)phenyl-3-methacrylamido-2-pyrazolin-5-one1-phenyl-3-methacrylamido-2-pyrazolin-5-onel-o-bromophenyl-3-methacrylamido-Z-pyrazolin- 5-one l-( 2 ,4 ,6-trichlorophenyl )-3-acrylamido-2-pyrazolin-5-onep-methacrylamidobenzoylacetanilide sulphonylamino-S-metha- 6 N-[3-methoxy-4-(o-methoxybenzoylacetylamino methacrylamidep-methacrylamido-benzoylacetaniside2-chloro-4-methacrylamido-benzoylacetanilidel-phenyl-3-methacrylamido-4-methyl-2-pyrazolin- 5-one1-p-methylsulphonylphenyl-3-methac rylamido-4- methyl-2-pyrazolin-5-one1-( 2-chloro-4-methylsulphonylphenyl)-3-methacrylamido-4-methyl-Z-pyrazolin-S-one 1-(2,4,6-trichlorophenyl)- ltrichlorophenyl )-3-methacrylamido-4-methyl-2-pyrazolin-5-onel-m-chlorophenyl-3-methacrylamido-4-methyl-2- pyrazolin-S-on The laticesof the polymeric colour forming couplers or competing couplers can beprepared by emulsion polymerization as described in Belgian Pat. No.669,971 and UK. Pat. No. 1,130,581 referred to above.

Examples of polymerization initiators and suitable solvents as well asinstructions relating to the formation of the initial emulsions and/orsuspensions are set forth in these Patents. 7

Amongst the polymerization initiators suitable for use in the aboveemulsion polymerization process may be mentioned: persulphates such asammonium and potassium persulphate, azonitrile compounds such as4,4-azo-bis(4-cyanovaleric acid) as well as peroxide compounds such asbenzoyl peroxide, hydrogen peroxide.

The aqueous dispersion of the polymerisable composition may optionallycontain conventional emulsifiers although they can be omitted and, ifused, can usually be employed in smaller proportion than is possiblewith known procedures where no comonomeric emulsifier is used.

The comonomeric sulphoesters and sulphoamides of acrylic acids anda-substituted acrylic acids are generally used in amounts ranging fromabout 0.5 to about 15, preferably from about 1 to about 10% by weightrelative to the weight of other polymerisable ethylenically unsaturatedmonomers.

The latices obtained generally comprise between about 2 and about 50 byweight of polymeric colour coupler or competing coupler in respect ofthe total amount of latex.

The polymeric couplers according to the present invention can be.characterized by their so-called equivalent molecular weight. Byequivalent molecular weight is understood the number of grams of polymercontaining 1 mole of polymerized monomeric coupler. It can be comparedwith the molecular weight of the non-polymeric classical non-migratorycouplers. The equivalent molecular weight of the polymeric couplersaccording to the invention can vary within very wide limits, preferablyfrom about 200 to about 2000.

The following preparations illustrate how the latices of the polymericcolour couplers and competing couplers of the present invention can beprepared.

PREPARATION 1 Latex of the copolymer ofl-phenyl-3-methacrylamido-4-methyl-2-pyrazolin-5-one, butylacrylate andthe sodium salt of 2-sulphoethyl methacrylate.

A suspension of 260 ml of demineralized water, 52.5 g of1-phenyl-3-methacrylamido-4-methyl-2-pyrazolin- 5-one and 37.5 ml of a10 aqueous solution of the sodium salt of 2-sulphoethylmethacrylate wasstirred for 30 min. while introducing nitrogen. The suspension washeated to 90C whereupon 6.75 g of n-butylacrylate and 8.5 ml ofa 1aqueous solution of the sodium salt of 4.4-azo-bis(4-cyanovaleric acid)were added. The temperature was raised to the reflux temperature andover a period of 30 min. were added 12 g of n-butylacrylate and 29 ml ofa 1 aqueous solution of the above polymerization initiator. The mixturewas refluxed for 1 hour and the latex obtained was cooled and filtered.

Yield 260 ml of very stable latex.

Concentration of solids per 100 ml of latex 24.2 g

Concentration of polymer per 100 ml of latex: 24.0 g

Equivalent molecular weight 342 PREPARATION 2 Latex of the copolymer ofl-p-methylsulphonylphenyl-3-methacrylamido-4-methyl-2-pyrazolin-5-one,butylacrylate and the sodium salt of 2-sulphoethyl methacrylate.

A suspension of 170 ml of demineralized water 40 g ofl-p-methylsulphonylphenyl-3-methacrylamido-4- methyl-2-pyrazolin-5-one,2.5 g of the sodium salt of 2-sulphoethylmethacrylate and 7.5 g ofbutylacrylate was heated to 90C whereupon 15 ml of a 1 aqueous solutionof the sodium salt of 4,4'-azo-bis(4-cyanovaleric acid) were added. Thetemperature was raised to the reflux temperature. The mixture wasrefluxed for 1 hour and the latex obtained was cooled and filtered.

Yield 250 ml of very stable latex.

Concentration of solids per 100 ml of latex 15.3

Concentration of polymer per 100 ml of latex: 15.2

Equivalent molecular weight 452 PREPARATION 3 Latex of the copolymer of1-phenyl-3-rnethacrylamido-Z-pyrazolin-5-one. butylacrylate and thesodium salt of 2-sulphoethyl methacrylate.

a. A suspension of 700 ml of demineralized water,

160 g of l-phenyl-3-methacrylamido-2-pyrazolin- 5-one and g of thesodium salt of 2-sulphoethyl methacrylate was stirred for 30 min. whileintroducing nitrogen and heated to 50C. After addition of 10 g ofbutylacrylate the mixture was heated to 90C and 25 ml of a l aqueoussolution of the sodium salt of 4,4-a2o-bis(4-cyanovaleric acid) wereadded.

The temperature rose to 95C and after 5 min.. g of butylacrylate and 75ml of the above solution of polymerization initiator were added dropwisein 30 min. The mixture was further stirred for 30 min. and then cooledand filtered.

Yield 800 m1 of very stable latex.

Concentration of solids per 100 ml of latex 20.75 g

Concentration of polymer per 100 ml of latex 20.6 g

Equivalent molecular weight 288 b. Another latex was prepared in asimilar way from 120 g of l-phenyl-3-methacrylamido-2-pyrazolin- 5-one.70 g of butyl acrylate and 5 g of the sodium salt of 2-sulphoethylmethacrylate.

Yield 800 ml of very stable latex.

Concentration of solids per 100 ml of latex 20.6 g

Concentration of polymer per 100 ml of latex: 20.5 g

Equivalent molecular weight 409 0. Another latex was prepared in asimilar way from 96 g of l-phenyl-3-methacrylamido-2-pyrazolin- 8 5-one.132 g of butylacrylate and 12 g of the sodium salt of 2-sulphoethylmethacrylate. Yield 800 ml of very stable latex. Concentration of solidsper 100 ml of latex 20.5 g Concentration of polymer per 100 ml of latex20.35

Equivalent molecular weight 640 PREPARATION 4 Latex of the copolymer ofl-benzyl-3-methacrylamido-Z-pyrazolin-S-one, styrene and the sodium saltof 2-sulphoethyl methacrylate.

A mixture of 175 ml of demineralized water, 20 g ofl-benzyl-3-methacrylamido-2-pyrazolin-5-one, 10 g of styrene and 2.5 gof the sodium salt of 2-sulphoethyl methacrylate was heated to 90C whileintroducing nitrogen.

After addition of 8 ml of a 1 aqueous solution of the sodium salt of4,4-azo-bis-(4-cyanovaleric acid) the mixture was left standing for 10min. whereupon 17.5 g of styrene and another 17 ml of the said 1 71aqueous solution were added dropwise while keeping the mixture at thereflux temperature. Refluxing was continued for min. and then the latexformed was cooled and filtered.

Yield 210 ml of very stable latex.

Concentration of solids per 100 ml of latex 14.00 g

Concentration of polymer per 100 ml of latex 13.9

Equivalent molecular weight 867.

PREPARATION 5 Latex of the copolymer of p-methacrylamidobenzoylacetaniside, butyl acrylate, methacrylic acid and the sodium salt of 2sulphoethyl methacrylate.

Nitrogen was introduced into a suspension of 300 ml of demineralizedwater, 40 g of p-methacrylamidobenzoyl acetaniside (mp 168C) preparedfrom p-aminobenzoyl acetaniside and methacryloyl chloride, and 50 ml ofa 10 aqueous solution of the sodium salt of 2-sulphoethyl methacrylate.The mixture was heated to C whereupon 12 g of methacrylic acid and 7 gof butyl acrylate were added. The temperature was raised to C and 25 mlof a l aqueous solution of the sodium salt of 4,4'-azo-bis(4cyanovalericacid) were added.

After 10 min., a mixture of 23 g of methacrylic acid and 13 g ofbutylacrylate was added dropwise in 30 min. with refluxing. After 30min. the latex formed was cooled and centrifuged.

Yield 390 ml of very stable latex.

Concentration of solids per ml of latex Concentration of polymer per 100ml of latex Equivalent molecular weight 995.

PREPARATION 6 30 min. Refluxing was continued for 30 min. and the latexobtained was cooled and centrifuged.

Yield 400 ml of very stable latex.

Concentration of solids per 100 ml of latex 19.5 g

Concentration of polymer per 100 ml of latex 19.4 g

Equivalent molecular weight 600 PREPARATION 7 Latex of the copolymer of2-methylsulphonylamino- 5-acrylamidophenol, butylacrylate and the sodiumsalt of 2-sulphoethyl methacrylate. This latex was prepared in the sameway as the latex of preparation 6 from 20 g of 2-methylsulphonylamino-S-acrylamidophenol, 27.5 g of butyl acrylate and 2.5 g ofthe sodium salt of 2-sulphoethyl methacrylate.

Yield 250 ml of very stable latex Concentration of solids per 100 ml oflatex: 15.10 g

Concentration of polymer per 100 ml of latex: 15.00

Equivalent molecular weight 707 PREPARATION 8 Latex of the copolymer of1-hydroxy-4-chloro-N-B- acrylamidoethyl-2-naphthamide, butylacrylate andthe sodium salt of 2-sulphoethylmethacrylate.

Nitrogen was introduced for 30 min. into a suspension of 350 ml ofdemineralized water, 50 g oflhydroxy-4-chloro-N-B-acrylamidoethyl-Z-naphthamide and 5 g of thesodium salt of 2-sulphoethyl methacrylate. The mixture was heated to 70Cand 15 g of butyl acrylate were added. The mixture was further heated to90C and 15 ml of a l aqueous solution of the sodium salt of4,4-azo-bis(4-cyanovaleric acid) were added. The mixture was refluxedfor 10 min. whereupon 30 g of butyl acrylate and 35 ml of the above 1aqueous solution were added. After 30 min., the latex was cooled andfiltered.

Yield 400 ml of very stable latex Concentration of solids per 100 ml oflatex 15.6 g

Concentration of polymer per 100 ml of latex 15.5

Equivalent molecular weight 851 PREPARATION 9 Latex of the copolymer ofl-phenyl-3-methacrylamido-2-pyrazolin-5-one, butylacrylate and thesodium salt of p-sulphophenyl methacrylate.

A suspension of 350 ml of distilled water, 40 g ofl-phenyl-3-methacrylamido-2-pyrazolin-5-one, and 5 g of the sodium saltof p-sulphophenyl methacrylate was rinsed with nitrogen for 30 min. andthen heated to 90C. Then, 25 g of butyl acrylate and 25 ml of a laqueous solution of the sodium salt of 4,4'-azobis(4- cyanovaleric acid)were added. The mixture was refluxed for 5 min. and 30 g of butylacrylate and 25 ml of the said 1 aqueous solution were added in 30 min.Refluxing was continued for 30 min. whereupon the latex was filtered.

Yield 360 ml.

Concentration of solids per 100 ml of latex 10.9 g

Concentration of polymer per 100 ml of latex: 10.7 g

Equivalent molecular weight 1 130.

PREPARATION l0 Latex of the copolymer of1-phenyl-3-methacrylamido-2-pyrazolin-5-one, butyl acrylate and thesodium salt of N-2-sulphoethyl methacrylamide.

Nitrogen was introduced into a suspension of 175 ml of water, 30 g ofl-phenyl-3-methacrylamido-2-pyrazolin-S-one, 5 g of butylacrylate and2.5 g of the sodium salt of N-2-sulphoethyl methacrylamide. The mixturewas heated to C and 5 ml of a 1 aqueous solution of the sodium salt of4,4-azo-bis(4-cyanovaleric acid) were added. The temperature was raisedto the reflux temperature and in 30 min., 12.5 g of butyl acrylate and20 ml of the initiator solution were added. Refluxing was continued for30 min. whereupon the latex was partly concentrated by evaporation,cooled and filtered.

Yield 170 ml of latex.

Concentration of solids per ml of latex 15.9 g

Concentration of polymers per 100 ml oflatex: 15.8 g

Equivalent molecular weight 446.

The latices according to the present invention are used in photographiccolour elements either in a silver halide emulsion layer or ahydrophilic colloid layer in water-permeable relationship with the saidemulsion layer. The latices of polymeric colour couplers are preferablyincorporated in a silver halide emulsion layer whereas the latices ofpolymeric competing couplers are preferably incorporated in one or moreintermediate hydrophilic colloid layers in water-permeable relationshipwith the emulsion layers.

In dispersing the latices according to the invention into thehydrophilic colloid composition e.g. an aque ous gelatin solution or agelatino silver halide emulsion there can be dispensed with the use ofan external ballasting emulsifying agent or reduced amounts ofemulsifying agents can be used so that it is possible to reduce thethickness of the coated layers which results in increased sharpness. Thelatices according to the invention also produce less foam whenincorporated into the hydrophilic colloid coating composition.

For example, when the latices of preparations 3a, 4, 5, 6 and 8hereinbefore were admixed with a conventional photographic silver halidecolour emulsion no supplemental amount of emulsifier was necessary tostabilize the latex polymer in the emulsion. As shown in the followingtable, the latices corresponding to those of preparations 3a, 4,5,6, and8 but prepared in the conventional way, i.e. in the presence of 5 g ofsodium oleyl methyl tauride (OMT) per 100 g of monomers used instead ofthe sodium salt of 2-sulphoethyl methacrylate, required a supplementalamount of OMT to be stabilised in the emulsion.

These conventional polymeric coupler latices also produced more foam asis illustrated in the following table. The volume foaming was measuredaccording to the Ross-Miles method (ASTM D 1173/53) after 0 and 5 min.

In the following table, the conventional latices corresponding to thoseof preparations 3a, 4,5,6 and 8 are designated A to E respectively.

. Table-continued Latex Amount of emulsivolume fier ballast in foaming gper I g polymer 0 min. min.

E l0 l6 14 The polymeric couplers of the present invention may be usedin various kinds of photographic colour materials which includenegative, positive as well as reversal material. Photographic multilayercolour materials usually comprise at least one blue-sensitive silverhalide emulsion layer with colour coupler for yellow, at least onegreen-sensitized silver halide emulsion layer with colour coupler formagenta and at least one red-sensitized silver halide emulsion layerwith colour coupler for cyan. These colour materials may furthercomprise one or more intermediates layers, filter layers and protectivesurface layers.

The hydrophilic colloid used as the vehicle for the silver halideemulsion layer and the other hydrophilic colloid layers may be, forexample, gelatin, colloidal albumin, zein, casein, a cellulosederivative, a synthetic hydrophilic colloid such as polyvinyl alcohol,poly-N- vinyl pyrr'olidone, etc., gelatin being preferred. If desiredcompatible mixtures of two or more of these colloids may be employed.

The silver halide emulsion layer may comprise various silver halides asthe sensitive halide such as silver bromide, silver chloride, silverchlorobromide, silver bromoiodide and silver chlorobromoiodide.

The photographic colour elements comprising the polymeric couplers ofthe present invention may comprise as supports paper, glass, celluloseester film, polyvinylacetal film, polystyrene film, polyethyleneterephthalate film and related films of resinous materials.

In the development of the exposed photographic colour materials aromaticprimary amino developing agents are used forming dyestuffs with thepolymeric colour couplers of the present invention and colourlesscompounds with the polymeric competing couplers of the presentinvention. Suitable developing agents are p-phenylene diamine andderivatives e.g. N,N-diethylp-phenylene diamine,N-butylN-sulphobutyl-p-phenylene diamine,2-amino-S-diethyIamino-toluene, 4- amino-N-ethyl-N( B-methanesulphonamidoethyl )-mtoluidine, N-hydroxyethyl-N-ethyl-p-phenylenediamiie etc.

The following examples illustrate the present invention.

EXAMPLE 1 a. Comparison material A 109 g of a silver bromoiodideemulsion (2.3 mole of iodide) which comprises per kg an amount of silverhalide equivalent to 47 g of silver nitrate and 73.4 g of gelatin, arediluted with 185 g of a 7.5 aqueous solution of gelatin and 100 g ofdistilled water. To the emulsion obtained are added with stirring 23 mlof the latex prepared according to preparation 6 of British Pat.application No. 59792/60 which corresponds to 0.006 mole of polymerisedmonomeric colour coupler. After the addition of the common additivessuch as stabilizers, wetting agents and hardeners the necessary amountof distilled water is added to obtain 575 g.

The emulsion obtained is coated on a cellulose triacetate support prorata of 125 g per sq.m. The emulsion 12 layer is dried and overcoatedwith a gelatin antistress layer. b. Material B2-amino-5-diethylaminotoluene hydrochloride Calgon anhydrous sodiumsulphite anhydrous sodium carbonate potassium bromide water to makelitre (pH: I065) The developed materials were treated for 5 min. at 24Cin an acid hardening fixer of the following composition:

water 800 ml anhydrous sodium thiosulphate 200 g sodium bisulphite 12 gglacial acetic acid 12 ml borax l0 aq. 20 g potassium alum 15 g water tomake I000 ml (pH:4.l0)

The materials were rinsed for 10 min. with water and treated in a bleachbath of the following composition:

anhydrous potassium bromide 20 g potassium alum 5 g potassium dichromate5 g water to make I litre (pH:3.l

After bleaching, the materials were rinsed with water for 5 min. andtreated for 5 min. at 24C in the above acid hardening fixer.

After a final rinsing for 10 min. the materials were dried.

Cyan coloured wedge images were obtained and the sensitometric resultsare listed in the table.

Table material relative speed gamma D A l 00 l .25 2 .04 B l 32 l .933.70

The above results show that the latex of the invention provides higherspeed, gamma and maximum density.

EXAMPLE 2 l 17 g of a silver bromoiodide emulsion (2.3 mole of iodide)which comprises per kg an amount of silver halide equivalent to 47 g ofsilver nitrate and 73.4 g of gelatin, are diluted with 192.5 g of a 7.5aqueous solution of gelatin and g of distilled water. To the emulsionobtained are added with stirring 12 ml of the latex. prepared accordingto preparation 3b which corresponds to 0.006 mole of polymerisedmonomeric colour coupler. After the addition of the common additivessuch as stabilizers, wetting agents and hardeners the necessary amountof distilled water is added to obtain 720 g.

The emulsion obtained is coated on a cellulose triacetate support prorata of l25 g per sq.m. The emulsion layer is dried and overcoated witha: gelatin antistress layer. g

After drying the material formed is exposed for 1/20 sec. through acontinuous wedge with constant 0.30 and then processed as described inexample 1.

A magenta wedge image was obtained.

EXAMPLE 3 A material was prepared as described in example 1 with thedifference that now 48 ml of the latex prepared according to preparation5, which corresponds to 0.006 mole of polymerised monomeric colourcoupler were added.

After drying the material formed was exposed to 1/20 sec. through acontinuous wedge with constant 0.30 and then developed for 8 min. at 20Cin a developing bath of the following composition:

N.N-diethyl-p-phenylene diamine sulphate hydroxylamine sulphate sodiumhexametaphosphate anhydrous sodium sulphite anhydrous potassiumcarbonate potassium bromide water to make The developed material wastreated for 2 min. at l820C in an intermediate bath comprising 30 g ofsodium sulphate in 1 liter of water.

The material was rinsed for 15 min. with water and treated in a bleachbath of the following composition:

borax 20 g potassium bromide l5 g anhydrous potassium bisulphate 4.2 gpotassium hexacyanoferrate(lll) g water to make I litre After bleaching,the material was rinsed with water for min. and fixed in an aqueoussolution of 200 g of sodium thiosulphate per liter.

After a final rinsing for min. the material was dried.

A yellow coloured wedge image was obtained.

EXAMPLE 4 A photographic multilayer negative material A was composed asfollows:

1. a common film support,

2. two red-sensitized silver halide emulsion layers each containing acolour coupler for cyan and a mask-forming compound, the undermostemulsion layer being of lower speed than the uppermost emulsion layer,

3. an intermediate gelatin layer,

4. two green-sensitized silver halide emulsion layers each containing acolour coupler for magenta and a mask-forming compound, the undermostemulsion layer being of lower speed than the uppermost emulsion layer,

5. a yellow gelatin filter layer,

6. two non-spectrally sensitized blue-sensitive silver halide emulsionlayers each containing a yellowforming colour coupler, the uppermostemulsion V14 layer having higher speed than the undermost emulsionlayer,and

7. a protective gelatin coating For comparison purposes a material Bwasprepared in exactly the same way as material A with the only differencethat both the gelatin-intermediate layer and the filter layer compriseper sq.m ,3 ml of the latex of the polymericcompeting coupler accordingto preparation 2, which corresponds to l millimole of polymerizedmonomeric coupler.

Samples of both materials were exposed to a wedge through a blue, greenand red filter and subjected to common negative colour processing forthe formation of the yellow, magenta and cyan separation images. Thedeveloping agent used was 2-amino-5-[N-ethyl-N(B-methylsulphonylamino)ethyl]amino toluene sulphate.

The separation images of material B showed purer colours than those ofmaterial A.

We claim:

1. A photographic colour element comprising a support and at least onelight-sensitive silver halide emulsion layer wherein the elementcomprises a copolymer latex containing recurring units derived from afirst ethylenically unsaturated monomer which will undergo oxidativecoupling with an aromatic primary amino compound corresponding to theformula:

wherein:

R is hydrogen, C C., alkyl or chlorine, and Q is a moiety which willundergo oxidative coupling with an aromatic primary amino compound, andrecurring units derived from a second monomer corresponding to theformula:

wherein:

R is hydrogen, C -C alkyl or chlorine,

X is O or N(R) wherein R is hydrogen or lower alkyl,

Y is a divalent hydrocarbon group which may be interrupted by oxygenand/or sulphur, and

M is a cation.

2. A photographic element according to claim 1, wherein in the saidformula Y represents a straightchain or branchedchain C -C alkylenegroup.

3. A photographic element according to claim 2, wherein in the saidformula X is -O.

4. A photographic element according to claim 1, wherein in the saidformula Q is a moiety of a phenol, naphthol, pyrazolone, indazolon oracylacetamide coupler.

5. A photographic element according to claim 1, wherein the polymercomprises recurring units of additional ethylenically unsaturatedmonomers which are not capable of oxidative coupling with aromaticprimary amino compounds.

6. A photographic element according to claim 5, wherein the saidadditional monomers are one or more members selected from the groupconsisting of acrylic 16 colour coupler and is present in alight-sensitive silver halide emulsion layer.

9. A photographic element according to claim 1, wherein the saidpolymeric compound is a polymeric competing coupler and is present in anintermediate non-light-sensitive water-permeable colloid layer of thephotographic element.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTIONPATENT NO. I 3, 926, 4:36

DATED December 16, 1975 INVENTOR(S) I Marcel Jacob MONBALIU ET AL It iscertified that error appears in the ab0ve-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Title Page, in the heading, the Assignee should read Agfa -Gevaert,

N.Va lVIortsel, Belgium Title Page, in the heading, "Attorney, Agent, orFirm Robert M.

Ashen; Robert J. Schaap" should read A. W. Breiner Column 5, line 7,"group" should read groups Column 6, line 11 should read l-(2,4,6-trichloropheny1)-3- Column 7, line 4, after "added" insert Column 14,claim 2, line 52, "branchedchain" should read branchedchain Signed andScaled this Twenty-eighth Day of June 1977 [SEAL] Arrest:

O RUTH c. MASON c. MARSHALL DANN Ar esting Office Commissioneroj'larenrs and Trademarks E

1. A PHOTOGRAPHIC COLOUR ELEMENT COMPRISING A SUPPORT AND AT LEAST ONELIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER WHEREIN THE ELEMENTCOMPRISES A COPOLYMER LATEX CONTAINING RECURRING UNITS DERIVED FROM AFIRST ETHYLENICALLY UNSATURATED MONOMER WHICH WILL UNDERGO OXIDATIVECOUPLING WITH AN AROMATIC PRIMARY AMINO COMPOUND CORRESPONDING TO THEFORMULA:
 2. A photographic element according to claim 1, wherein in thesaid formula Y represents a straight-chain or branchedchain C2-C4alkylene group.
 3. A photographic element according to claim 2, whereinin the said formula X is -O-.
 4. A photographic element according toclaim 1, wherein in the said formula Q is a moiety of a phenol,naphthol, pyrazolone, indazolon or acylacetamide coupler.
 5. Aphotographic element according to claim 1, wherein the polymer comprisesrecurring units of additional ethylenically unsaturated monomers whichare not capable of oxidative coupling with aromatic primary aminocompounds.
 6. A photographic element according to claim 5, wherein thesaid additional monomers are one or more members selected from the groupconsisting of acrylic acid, methacrylic acid, esters and amides derivedfrom these acids and styrene and its derivatives.
 7. A photographicelement according to claim 1, wherein the polymeric compound isincorporated into the coating composition of the said emulsion layer orhydrophilic colloid layer from an aqueous dispersion (latex).
 8. Aphotographic element according to claim 1, wherein the said polymericcompound is a polymeric colour coupler and is present in alight-sensitive silver halide emulsion layer.
 9. A PHOTOGRAPHIC ELEMENTACCORDING TO CLAIM 1, WHEREIN THE SAID POLYMERIC COMPOUND IS A POLYMERICCOMPETING COUPLER AND IS PRESENT IN AN INTERMEDIATE NON-LIGHT-SENSITIVEWATER-PERMEABLE COLLOID LAYER OF THE PHOTOGRAPHIC ELEMENT.